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Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.

Journal Article


Abstract


  • Dirhenium halide dianions received considerable attention in past decades due to the unusual metal-metal quadruple bond. The systematic structural evolution of dirhenium halide clusters has not been sufficiently studied and hence is not well-understood. In this work, we report an in-depth investigation on the structures and electronic properties of doubly charged dirhenium halide clusters Re2X82- (X = F, Cl, Br, I). Our computational efforts rely on the well-tested unbiased CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) method combined with density functional theory calculations. We find that all ground-state Re2X82- clusters have cube-like structures of D4h symmetry with two Re atoms encapsulated in halogen framework. The reasonable agreement between the simulated and experimental photoelectron spectrum of the Re2Cl82- cluster supports strongly the reliability of our computational strategy. The chemical bonding analysis reveals that the δ bond is the pivotal factor for the ground-state Re2X82- (X = F, Cl, Br, I) clusters to maintain D4h symmetric cube-like structures, and the enhanced stability of Re2Cl82- is mainly attributed to the chemical bonding of 5d orbital of Re atoms and 3p orbital of Cl atoms.

Publication Date


  • 2018

Citation


  • Zhang, L. H., Xia, X. X., Sun, W. G., Lu, C., Kuang, X. Y., Le Chen, B., & Maroulis, G. (2018). Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.. Scientific reports, 8(1), 6702. doi:10.1038/s41598-018-25027-1

Web Of Science Accession Number


Start Page


  • 6702

Volume


  • 8

Issue


  • 1

Abstract


  • Dirhenium halide dianions received considerable attention in past decades due to the unusual metal-metal quadruple bond. The systematic structural evolution of dirhenium halide clusters has not been sufficiently studied and hence is not well-understood. In this work, we report an in-depth investigation on the structures and electronic properties of doubly charged dirhenium halide clusters Re2X82- (X = F, Cl, Br, I). Our computational efforts rely on the well-tested unbiased CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) method combined with density functional theory calculations. We find that all ground-state Re2X82- clusters have cube-like structures of D4h symmetry with two Re atoms encapsulated in halogen framework. The reasonable agreement between the simulated and experimental photoelectron spectrum of the Re2Cl82- cluster supports strongly the reliability of our computational strategy. The chemical bonding analysis reveals that the δ bond is the pivotal factor for the ground-state Re2X82- (X = F, Cl, Br, I) clusters to maintain D4h symmetric cube-like structures, and the enhanced stability of Re2Cl82- is mainly attributed to the chemical bonding of 5d orbital of Re atoms and 3p orbital of Cl atoms.

Publication Date


  • 2018

Citation


  • Zhang, L. H., Xia, X. X., Sun, W. G., Lu, C., Kuang, X. Y., Le Chen, B., & Maroulis, G. (2018). Probing the Structural and Electronic Properties of Dirhenium Halide Clusters: A Density Functional Theory Study.. Scientific reports, 8(1), 6702. doi:10.1038/s41598-018-25027-1

Web Of Science Accession Number


Start Page


  • 6702

Volume


  • 8

Issue


  • 1